Personal care formulation

ABSTRACT

A personal care formulation is provided comprising: multistage polymer, comprising: acrylate rich stage comprising: (a) structural units of monoethylenically unsaturated non-ionic, acrylate rich stage monomer selected from C1-22 alkyl (meth)acrylates and mixtures thereof; and (b) carbosiloxane rich stage, comprising: structural units of carbosiloxane monomer of formula (I), wherein a is 0 to 3; wherein d is 0 or 1; wherein R1 is selected from hydrogen, C1-10 alkyl group and aryl group; wherein R2 is selected from hydrogen and C1-10 alkyl group; wherein R8 is —O—Si(CH3)2—O—Si(CH3)3 group; wherein Y is selected from formula (II), (III) and (IV); wherein R4 and R6 are selected from hydrogen and methyl group; wherein R3 and R5 are a C1-10 alkylene group; wherein R7 is C1-10 alkyl group; wherein b is 0 to 4 and wherein c is 0 or 1.

The present invention relates to a personal care formulation. Inparticular, the present invention relates to a personal care formulationincluding a multistage polymer, comprising: an acrylate rich stagecomprising: (a) structural units of monoethylenically unsaturatednon-ionic, acrylate rich stage monomer selected from C₁₋₂₂ alkyl(meth)acrylates and mixtures thereof; and (b) a carbosiloxane richstage, comprising: structural units of carbosiloxane monomer of formula(I), wherein a is 0 to 3; wherein d is 0 or 1; wherein R¹ is selectedfrom hydrogen, C₁₋₁₀ alkyl group and aryl group; wherein R² is selectedfrom hydrogen and C₁₋₁₀ alkyl group; wherein R⁸ is—O—Si(CH₃)₂—O—Si(CH₃)₃ group; wherein Y is selected from formula (II),(III) and (IV); wherein R⁴ and R⁶ are selected from hydrogen and methylgroup; wherein R³ and R⁵ are a C₁₋₁₀ alkylene group; wherein R⁷ is C₁₋₁₀alkyl group; wherein b is 0 to 4 and wherein c is 0 or 1.

Consumers desire personal care formulations that provide long wearproperties, such that the formulation might be applied once and lastthrough the work day and beyond without the need for refreshing ortouching up. Given todays active lifestyles, it is no simple task toprovide such long wear personal care formulations.

In addition, the damaging effects of sunlight on human skin are welldocumented. Six percent of the solar energy reaching the Earth's surfaceis ultraviolet (UV) radiation having a wavelength of 290 to 400 nm. Thisradiation is divided into two components: (i) low energy UVA radiationhaving a wavelength of 320 to 400 nm and (ii) high energy UVB radiationhaving a wavelength of 290 to 320 nm. While the UV portion of solarenergy is relatively small, it induces nearly 99% of all the sideeffects from sunlight exposure. High energy UVB radiation, for example,is responsible for producing sunburn, appearance of skin aging and skincancer. Low energy UVA radiation, for example, is responsible forinducing direct tanning and erythema (abnormal redness) of the skin andcontributes to the appearance of skin aging.

By avoiding direct exposure to sunlight, individuals can avoid theserious effects caused by exposure to UV radiation. However, because ofthe nature of their work, it is challenging for some people to avoidsuch exposure. In addition, some people voluntarily expose their skin tothe sun, e.g., to tan. Therefore, protection against the harmful effectsof the sun is important.

Protection from the harmful effects of UV radiation exposure isavailable in the form of both topically applied formulations containingat least one physical UV blocker, or at least one chemical UV absorber,or combinations thereof. Physical blockers include active ingredientssuch as, titanium dioxide, zinc oxide and red petrolatum. Chemicalabsorbers include active ingredients, such as, paraaminobenzoic acid(more commonly known as PABA), which are generally transparent whenapplied and act by absorbing UV radiation, offering selective protectionagainst certain UV wave bands, depending on the absorption spectrum ofthe active ingredient in the formulation.

The effectiveness of a given personal care formulation is assessed byhow well it protects the skin in terms of a Sun Protection Factor (SPF)which is defined as the ratio of the amount of energy required toproduce a minimal erythema on sunscreen protected skin to the amount ofenergy required to produce the same level of erythema on unprotectedskin.

Some of the chemical absorbers and physical blockers (e.g., suncareactives) typically used in sunscreen formulations reportedly haveadverse toxicological effects and negative sensory effects, whichdiscourage people from using sunscreens. Therefore, it is desirable toreduce the level of suncare actives present in sunscreen formulationswithout reducing the SPF protection. Accordingly, a variety of SPFboosters have been developed for use in suncare formulations to reducethe level of suncare actives without a reduction in the SPF protectionprovided. It is also desirable that personal care formulations exhibitwater resistance and retention of the suncare active ingredients inpersonal care formulations during use.

An approach to providing long wear formulations is disclosed by Konik etal. in U.S. Pat. No. 6,060,072. In U.S. Pat. No. 6,060,072, Konik et al.disclose water proof or water resistant cosmetic compositions whichcomprise a styrene-ethylene-propylene copolymer in an amount of 5 to10%, a combination of a PVP/eicosene copolymer and tricontanyl PVPcopolymer in an amount of 0.1 to 50%, a C₈₋₉ isoparaffin, a C₉₋₁₂aliphatic hydrocarbon, or a combination thereof, in an amount of 50 to85%.

Notwithstanding, there remains a need for new personal care formulationsthat provide long wear properties and offer an effective SPF ratingwhile reducing the necessary incorporation level of UV absorbing agentsand exhibit water resistance and suncare active retention.

The present invention provides a personal care formulation, comprising:a multistage polymer, comprising: (a) an acrylate rich stage comprising:88 to 100 wt %, based on weight of the acrylate rich stage, ofstructural units of a monoethylenically unsaturated non-ionic, acrylaterich stage monomer, wherein the monoethylenically unsaturated non-ionic,acrylate rich stage monomer is selected from the group consisting ofC₁₋₂₂ alkyl (meth)acrylates and mixtures thereof; 0 to 10 wt %, based onweight of the acrylate rich stage, of structural units of amonoethylenically unsaturated carboxylic acid, acrylate rich stagemonomer; and 0 to 2 wt %, based on weight of the acrylate rich stage, ofstructural units of a multiethylenically unsaturated, acrylate richstage monomer having at least two ethylenically unsaturated groups permolecule; and (b) a carbosiloxane rich stage, comprising: 0 to 90 wt %,based on weight of the carbosiloxane rich stage, of structural units ofa vinyl monomer; and 10 to 100 wt %, based on weight of thecarbosiloxane rich stage, of structural units of a carbosiloxane monomerof formula (I)

wherein a is 0 to 3; wherein d is 0 or 1; wherein each IV isindependently selected from the group consisting of a hydrogen, a C₁₋₁₀alkyl group and an aryl group; wherein each R² is independently selectedfrom the group consisting of a hydrogen and a C₁₋₁₀ alkyl group; whereineach R⁸ is a —O—Si(CH₃)₂—O—Si(CH₃)₃ group; wherein Y is selected fromthe group consisting of formula (II), (III) and (IV)

wherein each R⁴ and R⁶ are independently selected from the groupconsisting of a hydrogen and a methyl group; wherein each R³ and R⁵ areindependently a C₁₋₁₀ alkylene group; wherein each R⁷ is independently aC₁₋₁₀ alkyl group; wherein b is 0 to 4 and wherein c is 0 or 1.

The present invention provides a personal care formulation, comprising:a multistage polymer, comprising: (a) an acrylate rich stage comprising:88 to 99.99 wt %, based on weight of the acrylate rich stage, ofstructural units of a monoethylenically unsaturated non-ionic, acrylaterich stage monomer, wherein the monoethylenically unsaturated non-ionic,acrylate rich stage monomer is selected from the group consisting of amixture of (i) 40 to 75 wt % of a C₁₋₄ alkyl (meth)acrylate and (ii) 25to 60 wt % of a C₆₋₂₂ alkyl (meth)acrylate selected from the groupconsisting of ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl(meth)acrylate, cetyl-eicosyl (meth)acrylate, behenyl (meth)acrylate andmixtures thereof; 0 to 10 wt %, based on weight of the acrylate richstage, of structural units of a monoethylenically unsaturated carboxylicacid, acrylate rich stage monomer; and 0.01 to 2 wt %, based on weightof the acrylate rich stage, of structural units of a multiethylenicallyunsaturated, acrylate rich stage monomer having at least twoethylenically unsaturated groups per molecule; and (b) a carbosiloxanerich stage, comprising: 10 to 50 wt %, based on weight of thecarbosiloxane rich stage, of structural units of a vinyl monomer; and 50to 90 wt %, based on weight of the carbosiloxane rich stage, ofstructural units of a carbosiloxane monomer of formula (I); wherein a is1; wherein d is 0; wherein each R¹ is a methyl group; wherein each R² isa methyl group; wherein Y is of formula (II); wherein each R⁴ is amethyl group; and wherein each R³ is a C₃₋₅ alkylene group.

The present invention provides a method of treating the skin of amammal, comprising: providing a personal care formulation of the presentinvention, applying the personal care formulation to the skin of amammal.

DETAILED DESCRIPTION

We have identified a unique multistage polymer composition havingdesirable properties for use in personal care formulations, inparticular for use in suncare formulations and color cosmeticformulations.

Unless otherwise indicated, ratios, percentages, parts, and the like areby weight.

The term “aesthetic characteristics” as used herein and in the appendedclaims in reference to a personal care formulation refers to visual andtactile sensory properties (e.g., smoothness, tack, lubricity, texture,color, clarity, tubridity, uniformity).

The term “structural units” as used herein and in the appended claimsrefers to the remnant of the indicated monomer in the claimed polymer;thus a structural unit of n-butyl acrylate is illustrated:

where the dotted lines represent the points of attachment to the polymerbackbone.

The term “(meth)acrylic acid” as used herein and in the appended claimsis intended to serve as a generic expression embracing both acrylic acidand methacrylic acid.

The term “(meth)acrylate” as used herein and in the appended claims isintended to serve as a generic expression embracing both acrylate andmethacrylate.

The term “cosmetically acceptable” as used herein and in the appendedrefers to ingredients that are typically used for topical application tothe skin, and is intended to underscore that materials that are toxicwhen present in the amounts typically found in skin care compositionsare not contemplated as part of the present invention.

Preferably, the personal care formulation of the present invention,comprises: a multistage polymer, comprising: (a) (preferably, 60 to 95wt % (more preferably, 65 to 90 wt %; still more preferably, 70 to 85 wt%; most preferably, 75 to 82 wt %), based on weight of the multistagepolymer, of) an acrylate rich stage comprising: 88 to 100 wt %(preferably, 94 to 99.49 wt %; more preferably, 97 to 99.23 wt %; stillmore preferably, 97.9 to 98.95 wt %; most preferably, 97.45 to 98.05 wt%), based on weight of the acrylate rich stage, of structural units of amonoethylenically unsaturated non-ionic, acrylate rich stage monomer,wherein the monoethylenically unsaturated non-ionic, acrylate rich stagemonomer is selected from the group consisting of C₁₋₂₂ alkyl(meth)acrylates and mixtures thereof; 0 to 10 wt % (preferably, 0.5 to 5wt %; more preferably, 0.75 to 2.5 wt %; still more preferably, 1 to 2wt %; most preferably, 1.25 to 1.75 wt %), based on weight of theacrylate rich stage, of structural units of a monoethylenicallyunsaturated carboxylic acid, acrylate rich stage monomer; and 0 to 2 wt% (preferably, 0.01 to 1 wt %; more preferably, 0.02 to 0.5 wt %; stillmore preferably, 0.05 to 0.1 wt %; most preferably, 0.07 to 0.08 wt %),based on weight of the acrylate rich stage, of structural units of amultiethylenically unsaturated, acrylate rich stage monomer having atleast two ethylenically unsaturated groups per molecule; and (b)(preferably, 5 to 40 wt % (more preferably, 10 to 35 wt %; still morepreferably, 15 to 30 wt %; most preferably, 18 to 25 wt %), based onweight of the multistage polymer, of) a carbosiloxane rich stage,comprising: 0 to 90 wt % (preferably, 10 to 50 wt %; more preferably,12.5 to 30 wt %; still more preferably, 15 to 25 wt %; most preferably,19 to 21 wt %), based on weight of the carbosiloxane rich stage, ofstructural units of a vinyl monomer; and 10 to 100 wt % (preferably, 50to 90 wt %; more preferably, 70 to 87.5 wt %; still more preferably, 75to 85 wt %; most preferably, 79 to 81 wt %), based on weight of thecarbosiloxane rich stage, of structural units of a carbosiloxane monomerof formula (I)

wherein a is 0 to 3 (preferably, 0 to 2; most preferably, 1); wherein dis 0 or 1 (preferably, 0); wherein each R¹ is independently selectedfrom the group consisting of a hydrogen, a C₁₋₁₀ alkyl group and an arylgroup (preferably, a hydrogen and a C₁₋₁₀ alkyl group; more preferably,a hydrogen and a C₁₋₄ alkyl group; still more preferably, a hydrogen anda methyl group; most preferably, a methyl group); wherein each R² isindependently selected from the group consisting of a hydrogen and aC₁₋₁₀ alkyl group (preferably, a hydrogen and a C₁₋₅ alkyl group; morepreferably, a hydrogen and a C₁₋₄ alkyl group; still more preferably, ahydrogen and a methyl group; most preferably, a methyl group); whereineach R⁸ is a —O—Si(CH₃)₂—O—Si(CH₃)₃ group; wherein Y is selected fromthe group consisting of formula (II), (III) and (IV) (preferably, (II)or (III); most preferably, (II))

wherein each R⁴ and R⁶ are independently selected from the groupconsisting of a hydrogen and a methyl group (preferably, a methylgroup); wherein each R³ and R⁵ are independently a C₁₋₁₀ alkylene group(preferably, a C₁₋₇ alkylene group; more preferably, a C₂₋₆ alkylenegroup; still more preferably, a C₃₋₅ alkylene group; most preferably, aC₃ alkylene group); wherein each R⁷ is independently a C₁₋₁₀ alkylgroup; wherein b is 0 to 4 and wherein c is 0 or 1.

Preferably, the personal care formulation of the present inventioncomprises a multistage polymer. More preferably, the personal careformulation of the present invention comprises: 0.1 to 10 wt %(preferably, 0.5 to 7.5 wt %; more preferably, 1 to 7 wt %; still morepreferably, 3 to 5 wt %; most preferably, 3.5 to 4.5 wt %) a multistagepolymer. Most preferably, the personal care formulation of the presentinvention comprises: 0.1 to 10 wt % (preferably, 0.5 to 7.5 wt %; morepreferably, 1 to 7 wt %; still more preferably, 3 to 5 wt %; mostpreferably, 3.5 to 4.5 wt %) a multistage polymer; wherein themultistage polymer, comprising an acrylate rich stage and acarbosiloxane rich stage.

Preferably, the multistage polymer of the present invention comprises anacrylate rich stage. More preferably, the multistage polymer of thepresent invention, comprises: 60 to 95 wt % (preferably, 65 to 90 wt %;more preferably, 70 to 85 wt %; most preferably, 75 to 82 wt %), basedon weight of the multistage polymer, of an acrylate rich stage. Mostpreferably, the multistage polymer of the present invention, comprises60 to 95 wt % (preferably, 65 to 90 wt %; more preferably, 70 to 85 wt%; most preferably, 75 to 82 wt %), based on weight of the multistagepolymer, of an acrylate rich stage; wherein the acrylate rich stage,comprises: 88 to 100 wt % (preferably, 94 to 99.49 wt %; morepreferably, 97 to 99.23 wt %; still more preferably, 97.9 to 98.95 wt %;most preferably, 97.45 to 98.05 wt %), based on weight of the acrylaterich stage, of structural units of a monoethylenically unsaturatednon-ionic, acrylate rich stage monomer; wherein the monoethylenicallyunsaturated non-ionic, acrylate rich stage monomer is selected from thegroup consisting of C₁₋₂₂ alkyl (meth)acrylates and mixtures thereof; 0to 10 wt % (preferably, 0.5 to 5 wt %; more preferably, 0.75 to 2.5 wt%; still more preferably, 1 to 2 wt %; most preferably, 1.25 to 1.75 wt%), based on weight of the acrylate rich stage, of structural units of amonoethylenically unsaturated carboxylic acid, acrylate rich stagemonomer; and 0 to 2 wt % (preferably, 0.01 to 1 wt %; more preferably,0.02 to 0.5 wt %; still more preferably, 0.05 to 0.1 wt %; mostpreferably, 0.07 to 0.08 wt %), based on weight of the acrylate richstage, of structural units of a multiethylenically unsaturated, acrylaterich stage monomer having at least two ethylenically unsaturated groupsper molecule.

Preferably, the acrylate rich stage comprises: 88 to 100 wt %(preferably, 94 to 99.49 wt %; more preferably, 97 to 99.23 wt %; stillmore preferably, 97.9 to 98.95 wt %; most preferably, 97.45 to 98.05 wt%), based on weight of the acrylate rich stage, of structural units of amonoethylenically unsaturated non-ionic, acrylate rich stage monomer;wherein the monoethylenically unsaturated non-ionic, acrylate rich stagemonomer is selected from the group consisting of C₁₋₂₂ alkyl(meth)acrylates and mixtures thereof. More preferably, the acrylate richstage comprises: 88 to 100 wt % (preferably, 94 to 99.49 wt %; morepreferably, 97 to 99.23 wt %; still more preferably, 97.9 to 98.95 wt %;most preferably, 97.45 to 98.05 wt %), based on weight of the acrylaterich stage, of structural units of a monoethylenically unsaturatednon-ionic, acrylate rich stage monomer, wherein the monoethylenicallyunsaturated non-ionic, acrylate rich stage monomer is selected from thegroup consisting of a mixture of at least two C₁₋₁₂ alkyl(meth)acrylates. Still more preferably, the acrylate rich stagecomprises: 88 to 100 wt % (preferably, 94 to 99.49 wt %; morepreferably, 97 to 99.23 wt %; still more preferably, 97.9 to 98.95 wt %;most preferably, 97.45 to 98.05 wt %), based on weight of the acrylaterich stage, of structural units of a monoethylenically unsaturatednon-ionic, acrylate rich stage monomer, wherein the monoethylenicallyunsaturated non-ionic, acrylate rich stage monomer is selected from thegroup consisting of a mixture of at least two C₁₋₈ alkyl(meth)acrylates. Yet more preferably, the acrylate rich stage comprises:88 to 100 wt % (preferably, 94 to 99.49 wt %; more preferably, 97 to99.23 wt %; still more preferably, 97.9 to 98.95 wt %; most preferably,97.45 to 98.05 wt %), based on weight of the acrylate rich stage, ofstructural units of a monoethylenically unsaturated non-ionic, acrylaterich stage monomer, wherein the monoethylenically unsaturated non-ionic,acrylate rich stage monomer is selected from the group consisting of amixture of at least three C₁₋₈ alkyl (meth)acrylates.

Preferably, the acrylate rich stage comprises: 88 to 100 wt %(preferably, 94 to 99.49 wt %; more preferably, 97 to 99.23 wt %; stillmore preferably, 97.9 to 98.95 wt %; most preferably, 97.45 to 98.05 wt%), based on weight of the acrylate rich stage, of structural units of amonoethylenically unsaturated non-ionic, acrylate rich stage monomer;wherein the monoethylenically unsaturated non-ionic, acrylate rich stagemonomer is selected from the group consisting of a mixture of (i) 40 to75 wt % (more preferably, 50 to 70 wt %; most preferably, 55 to 65 wt%), based on weight of the acrylate rich stage, of at least one C₁₋₅alkyl (meth)acrylate and (ii) 25 to 60 wt % (more preferably, 30 to 50wt %; most preferably, 35 to 45 wt %), based on weight of the acrylaterich stage, of at least one C₆₋₂₂ alkyl (meth)acrylate. More preferably,the acrylate rich stage comprises: 88 to 100 wt % (preferably, 94 to99.49 wt %; more preferably, 97 to 99.23 wt %; still more preferably,97.9 to 98.95 wt %; most preferably, 97.45 to 98.05 wt %), based onweight of the acrylate rich stage, of structural units of amonoethylenically unsaturated non-ionic, acrylate rich stage monomer;wherein the monoethylenically unsaturated non-ionic, acrylate rich stagemonomer is selected from the group consisting of a mixture of (i) 40 to75 wt % (more preferably, 50 to 70 wt %; most preferably, 55 to 65 wt%), based on weight of the acrylate rich stage, of at least one C₁₋₄alkyl (meth)acrylate selected from the group consisting of butyl(meth)acrylate, isobutyl (meth)acrylate, methyl (meth)acrylate andmixtures thereof; and (ii) 25 to 60 wt % (more preferably, 30 to 50 wt%; most preferably, 35 to 45 wt %), based on weight of the acrylate richstage, of at least one C₆₋₂₂ alkyl (meth)acrylate selected from thegroup consisting of ethylhexyl (meth)acrylate, lauryl (meth)acrylate,stearyl (meth)acrylate, cetyl-eicosyl (meth)acrylate, behenyl(meth)acrylate and mixtures thereof. Still more preferably, the acrylaterich stage comprises: 88 to 100 wt % (preferably, 94 to 99.49 wt %; morepreferably, 97 to 99.23 wt %; still more preferably, 97.9 to 98.95 wt %;most preferably, 97.45 to 98.05 wt %), based on weight of the acrylaterich stage, of structural units of a monoethylenically unsaturatednon-ionic, acrylate rich stage monomer; wherein the monoethylenicallyunsaturated non-ionic, acrylate rich stage monomer is selected from thegroup consisting of a mixture of (i) 40 to 75 wt % (more preferably, 50to 70 wt %; most preferably, 55 to 65 wt %), based on weight of theacrylate rich stage, of at least one C₁₋₄ alkyl (meth)acrylate selectedfrom the group consisting of butyl acrylate, butyl methacrylate isobutylmethacrylate, methyl methacrylate and mixtures thereof; and (ii) 25 to60 wt % (more preferably, 30 to 50 wt %; most preferably, 35 to 45 wt%), based on weight of the acrylate rich stage, of at least one C₆₋₂₂alkyl (meth)acrylate selected from the group consisting of ethylhexyl(meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate andmixtures thereof. Most preferably, the acrylate rich stage comprises: 88to 100 wt % (preferably, 94 to 99.49 wt %; more preferably, 97 to 99.23wt %; still more preferably, 97.9 to 98.95 wt %; most preferably, 97.45to 98.05 wt %), based on weight of the acrylate rich stage, ofstructural units of a monoethylenically unsaturated non-ionic, acrylaterich stage monomer; wherein the monoethylenically unsaturated non-ionic,acrylate rich stage monomer is selected from the group consisting of amixture of (i) 40 to 75 wt % (more preferably, 50 to 70 wt %; mostpreferably, 55 to 65 wt %), based on weight of the acrylate rich stage,of at least one C₁₋₄ alkyl (meth)acrylate selected from the groupconsisting of butyl acrylate, butyl methacrylate isobutyl methacrylate,methyl methacrylate and mixtures thereof; and (ii) 25 to 60 wt % (morepreferably, 30 to 50 wt %; most preferably, 35 to 45 wt %), based onweight of the acrylate rich stage, of at least one C₆₋₂₂ alkyl(meth)acrylate selected from the group consisting of ethylhexylacrylate, ethylhexyl methacrylate and mixtures thereof.

Preferably, the acrylate rich stage comprises: 0 to 10 wt % (preferably,0.5 to 5 wt %; more preferably, 0.75 to 2.5 wt %; still more preferably,1 to 2 wt %; most preferably, 1.25 to 1.75 wt %), based on weight of theacrylate rich stage, of structural units of a monoethylenicallyunsaturated carboxylic acid, acrylate rich stage monomer. Morepreferably, the acrylate rich stage comprises: 0 to 10 wt % (preferably,0.5 to 5 wt %; more preferably, 0.75 to 2.5 wt %; still more preferably,1 to 2 wt %; most preferably, 1.25 to 1.75 wt %), based on weight of theacrylate rich stage, of structural units of a monoethylenicallyunsaturated carboxylic acid, acrylate rich stage monomer; wherein themonoethylenically unsaturated carboxylic acid, acrylate rich stagemonomer is selected from the group consisting of (meth)acrylic acid,(meth)acryloxypropionic acid, itaconic acid, aconitic acid, maleic acid,maleic anhydride, fumaric acid, crotonic acid, citraconic acid, maleicanhydride, monomethyl maleate, monomethyl fumarate, monomethylitaconate, other derivatives (such as corresponding anhydride, amidesand esters) and mixtures thereof. Still more preferably, the acrylaterich stage comprises: 0 to 10 wt % (preferably, 0.5 to 5 wt %; morepreferably, 0.75 to 2.5 wt %; still more preferably, 1 to 2 wt %; mostpreferably, 1.25 to 1.75 wt %), based on weight of the acrylate richstage, of structural units of a monoethylenically unsaturated carboxylicacid, acrylate rich stage monomer; wherein the monoethylenicallyunsaturated carboxylic acid, acrylate rich stage monomer is selectedfrom the group consisting of acrylic acid, methacrylic acid, itaconicacid, crotonic acid and mixtures thereof. Yet more preferably, theacrylate rich stage comprises: 0 to 10 wt % (preferably, 0.5 to 5 wt %;more preferably, 0.75 to 2.5 wt %; still more preferably, 1 to 2 wt %;most preferably, 1.25 to 1.75 wt %), based on weight of the acrylaterich stage, of structural units of a monoethylenically unsaturatedcarboxylic acid, acrylate rich stage monomer; wherein themonoethylenically unsaturated carboxylic acid, acrylate rich stagemonomer is selected from the group consisting of at least one of acrylicacid and methacrylic acid. Most preferably, the acrylate rich stagecomprises: 0 to 10 wt % (preferably, 0.5 to 5 wt %; more preferably,0.75 to 2.5 wt %; still more preferably, 1 to 2 wt %; most preferably,1.25 to 1.75 wt %), based on weight of the acrylate rich stage, ofstructural units of a monoethylenically unsaturated carboxylic acid,acrylate rich stage monomer; wherein the monoethylenically unsaturatedcarboxylic acid, acrylate rich stage monomer is methacrylic acid.

Preferably, the acrylate rich stage comprises: 0 to 2 wt % (preferably,0.01 to 1 wt %; more preferably, 0.02 to 0.5 wt %; still morepreferably, 0.05 to 0.1 wt %; most preferably, 0.07 to 0.08 wt %), basedon weight of the acrylate rich stage, of structural units of amultiethylenically unsaturated, acrylate rich stage monomer having atleast two ethylenically unsaturated groups per molecule. Morepreferably, the acrylate rich stage comprises: 0 to 2 wt % (preferably,0.01 to 1 wt %; more preferably, 0.02 to 0.5 wt %; still morepreferably, 0.05 to 0.1 wt %; most preferably, 0.07 to 0.08 wt %), basedon weight of the acrylate rich stage, of structural units of amultiethylenically unsaturated, acrylate rich stage monomer having atleast two ethylenically unsaturated groups per molecule; wherein themultiethylenically unsaturated monomer having at least two ethylenicallyunsaturated groups per molecule is selected from the group consisting ofdivinylaromatic compounds, di-(meth)acrylate esters, tri-(meth)acrylateesters, tetra-(methacrylate)esters, di-allyl ethers, tri-allyl ethers,tetra-allyl ethers, di-allyl esters, tri-allyl esters, tetra-allylesters, allyl (meth)acrylate and mixtures thereof. Still morepreferably, the acrylate rich stage comprises: 0 to 2 wt % (preferably,0.01 to 1 wt %; more preferably, 0.02 to 0.5 wt %; still morepreferably, 0.05 to 0.1 wt %; most preferably, 0.07 to 0.08 wt %), basedon weight of the acrylate rich stage, of structural units of amultiethylenically unsaturated, acrylate rich stage monomer having atleast two ethylenically unsaturated groups per molecule; wherein themultiethylenically unsaturated monomer having at least two ethylenicallyunsaturated groups per molecule is selected from the group consisting ofdivinylbenzene (DVB), trimethylolpropane diallyl ether, tetra-allylpentaerythritol, triallyl pentaerythritol, diallyl pentaerythritol,dially phthalate, diallyl maleate, triallyl cyanurate, Bisphenol Adiallyl ether, allyl sucroses, methylene bisacrylamide,trimethylolpropane triacrylate, allyl methacrylate (ALMA), ethyleneglycol dimethacrylate (EGDMA), hexane-1,6-diol diacrylate (HDDA),butylene glycol dimethacrylate (BGDMA) and mixtures thereof. Yet morepreferably, the acrylate rich stage comprises: 0 to 2 wt % (preferably,0.01 to 1 wt %; more preferably, 0.02 to 0.5 wt %; still morepreferably, 0.05 to 0.1 wt %; most preferably, 0.07 to 0.08 wt %), basedon weight of the acrylate rich stage, of structural units of amultiethylenically unsaturated, acrylate rich stage monomer having atleast two ethylenically unsaturated groups per molecule; wherein themultiethylenically unsaturated monomer having at least two ethylenicallyunsaturated groups per molecule is selected from the group consisting ofDVB, ALMA, EGDMA, HDDA and BGDMA. Yet still more preferably, theacrylate rich stage comprises: 0 to 2 wt % (preferably, 0.01 to 1 wt %;more preferably, 0.02 to 0.5 wt %; still more preferably, 0.05 to 0.1 wt%; most preferably, 0.07 to 0.08 wt %), based on weight of the acrylaterich stage, of structural units of a multiethylenically unsaturated,acrylate rich stage monomer having at least two ethylenicallyunsaturated groups per molecule; wherein the multiethylenicallyunsaturated monomer having at least two ethylenically unsaturated groupsper molecule includes ALMA. Most preferably, the acrylate rich stagecomprises: 0 to 2 wt % (preferably, 0.01 to 1 wt %; more preferably,0.02 to 0.5 wt %; still more preferably, 0.05 to 0.1 wt %; mostpreferably, 0.07 to 0.08 wt %), based on weight of the acrylate richstage, of structural units of a multiethylenically unsaturated, acrylaterich stage monomer having at least two ethylenically unsaturated groupsper molecule; wherein the multiethylenically unsaturated monomer havingat least two ethylenically unsaturated groups per molecule is ALMA.

Preferably, the multistage polymer of the present invention comprises ancarbosiloxane rich stage. More preferably, the multistage polymer of thepresent invention, comprises: 5 to 40 wt % (preferably, 10 to 35 wt %;more preferably, 15 to 30 wt %; most preferably, 18 to 25 wt %), basedon weight of the multistage polymer, of a carbosiloxane rich stage. Mostpreferably, the multistage polymer of the present invention, comprises:5 to 40 wt % (preferably, 10 to 35 wt %; more preferably, 15 to 30 wt %;most preferably, 18 to 25 wt %), based on weight of the multistagepolymer, of a carbosiloxane rich stage; wherein the carbosiloxane richstage comprises: 0 to 90 wt % (preferably, 10 to 50 wt %; morepreferably, 12.5 to 30 wt %; still more preferably, 15 to 25 wt %; mostpreferably, 19 to 21 wt %), based on weight of the carbosiloxane richstage, of structural units of a vinyl monomer; and 10 to 100 wt %(preferably, 50 to 90 wt %; more preferably, 70 to 87.5 wt %; still morepreferably, 75 to 85 wt %; most preferably, 79 to 81 wt %), based onweight of the carbosiloxane rich stage, of structural units of acarbosiloxane monomer of formula (I).

Preferably, the carbosiloxane rich stage comprises: 0 to 90 wt %(preferably, 10 to 50 wt %; more preferably, 12.5 to 30 wt %; still morepreferably, 15 to 25 wt %; most preferably, 19 to 21 wt %), based onweight of the carbosiloxane rich stage, of structural units of a vinylmonomer. More preferably, the carbosiloxane rich stage comprises: 0 to90 wt % (preferably, 10 to 50 wt %; more preferably, 12.5 to 30 wt %;still more preferably, 15 to 25 wt %; most preferably, 19 to 21 wt %),based on weight of the carbosiloxane rich stage, of structural units ofa vinyl monomer; wherein the vinyl monomer contains at least oneradically polymerizable vinyl group per molecule. Still more preferably,the carbosiloxane rich stage comprises: 0 to 90 wt % (preferably, 10 to50 wt %; more preferably, 12.5 to 30 wt %; still more preferably, 15 to25 wt %; most preferably, 19 to 21 wt %), based on weight of thecarbosiloxane rich stage, of structural units of a vinyl monomer;wherein the vinyl monomer is selected from the group consisting of C₁₋₃alkyl acrylates (e.g., methyl acrylate, ethyl acrylate, n-propylacrylate, isopropyl acrylate); C₁₋₃ alkyl methacrylates (e.g., methylmethacrylate, ethyl methacrylate, n-propyl methacrylate, isopropylmethacrylate); monoethylenically unsaturated carboxylic acids (e.g.,(meth)acrylic acid, (meth)acryloxypropionic acid, itaconic acid,aconitic acid, maleic acid, maleic anhydride, fumaric acid, crotonicacid, citraconic acid, maleic anhydride, monomethyl maleate, monomethylfumarate, monomethyl itaconate); C₄₋₂₀ alkyl acrylates (e.g., n-butylacrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate,cyclohexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, laurylacrylate, stearyl acrylate); C₄₋₂₀ alkyl methacrylates (e.g., n-butylmethacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexylmethacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, octylmethacrylate, lauryl methacrylate, stearyl methacrylate); aromatic vinylmonomers (e.g., styrene, vinyl toluene, benzyl acrylate, benzylmethacrylate, phenoxyethyl acrylate, phenoxyethyl methacrylate, vinylpyrrolidone); and mixtures thereof. Yet more preferably, thecarbosiloxane rich stage comprises: 0 to 90 wt % (preferably, 10 to 50wt %; more preferably, 12.5 to 30 wt %; still more preferably, 15 to 25wt %; most preferably, 19 to 21 wt %), based on weight of thecarbosiloxane rich stage, of structural units of a vinyl monomer;wherein the vinyl monomer is selected from the group consisting ofmethyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate,methyl methacrylate, ethyl methacrylate, n-propyl methacrylate,isopropyl methacrylate, n-butyl acrylate, isobutyl acrylate, tert-butylacrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate,n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate,n-hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid andmixtures thereof. Most preferably, the carbosiloxane rich stagecomprises: 0 to 90 wt % (preferably, 10 to 50 wt %; more preferably,12.5 to 30 wt %; still more preferably, 15 to 25 wt %; most preferably,19 to 21 wt %), based on weight of the carbosiloxane rich stage, ofstructural units of a vinyl monomer; wherein the vinyl monomer includesmethyl methacrylate and methacrylic acid.

Preferably, the carbosiloxane rich stage comprises: 10 to 100 wt %(preferably, 50 to 90 wt %; more preferably, 70 to 87.5 wt %; still morepreferably, 75 to 85 wt %; most preferably, 79 to 81 wt %), based onweight of the carbosiloxane rich stage, of structural units of acarbosiloxane monomer of formula (I). More preferably, the carbosiloxanerich stage comprises: 10 to 100 wt % (preferably, 50 to 90 wt %; morepreferably, 70 to 87.5 wt %; still more preferably, 75 to 85 wt %; mostpreferably, 79 to 81 wt %), based on weight of the carbosiloxane richstage, of structural units of a carbosiloxane monomer of formula (I),wherein a is 0 to 3 (preferably, 0 to 2; most preferably, 1); wherein dis 0 or 1 (preferably, 0); wherein each R¹ is independently selectedfrom the group consisting of a hydrogen, a C₁₋₁₀ alkyl group and an arylgroup (preferably, a hydrogen and a C₁₋₁₀ alkyl group; more preferably,a hydrogen and a C₁₋₄ alkyl group; still more preferably, a hydrogen anda methyl group; most preferably, a methyl group); wherein each R² isindependently selected from the group consisting of a hydrogen and aC₁₋₁₀ alkyl group (preferably, a hydrogen and a C₁₋₅ alkyl group; morepreferably, a hydrogen and a C₁₋₄ alkyl group; still more preferably, ahydrogen and a methyl group; most preferably, a methyl group); whereineach R⁸ is a —O—Si(CH₃)₂—O—Si(CH₃)₃ group; wherein Y is selected fromthe group consisting of formula (II), (III) and (IV) (preferably, (II)or (III); most preferably, (II)); wherein each R⁴ and R⁶ areindependently selected from the group consisting of a hydrogen and amethyl group (preferably, a methyl group); wherein each R³ and R⁵ areindependently a C₁₋₁₀ alkylene group (preferably, a C₁₋₇ alkylene group;more preferably, a C₂₋₆ alkylene group; still more preferably, a C₃₋₅alkylene group; most preferably, a C₃ alkylene group); wherein each R⁷is independently a C₁₋₁₀ alkyl group; wherein b is 0 to 4 and wherein cis 0 or 1. Most preferably, the carbosiloxane rich stage comprises: 10to 100 wt % (preferably, 50 to 90 wt %; more preferably, 70 to 87.5 wt%; still more preferably, 75 to 85 wt %; most preferably, 79 to 81 wt%), based on weight of the carbosiloxane rich stage, of structural unitsof a carbosiloxane monomer of formula (I), wherein a is 1; wherein d is0; wherein each R¹ is a methyl group; wherein each R² is a methyl group;wherein Y is of formula (II); wherein each R³ is a C₃₋₅ alkylene group;and wherein each R⁴ is a methyl group.

Preferably, the personal care formulation of the present invention,further comprises a cosmetically acceptable carrier. More preferably,the personal care formulation of the present invention, comprises: 30 to92 wt % (preferably, 35 to 92 wt %; more preferably, 40 to 80 wt %) of acosmetically acceptable carrier. Most preferably, the personal careformulation of the present invention, comprises 30 to 92 wt %(preferably, 35 to 92 wt %; more preferably, 40 to 80 wt %) of acosmetically acceptable carrier; wherein the multistage polymer isdispersed in the cosmetically acceptable carrier.

Preferably, the personal care formulation of the present invention,comprises 30 to 92 wt % (preferably, 35 to 92 wt %; more preferably, 40to 80 wt %) of a cosmetically acceptable carrier; wherein thecosmetically acceptable carrier is selected to be capable of evaporatingupon application of the personal care formulation to mammalian skin(preferably, human skin).

Preferably, the personal care formulation of the present invention,comprises 30 to 92 wt % (preferably, 35 to 92 wt %; more preferably, 40to 80 wt %) of a cosmetically acceptable carrier; wherein thecosmetically acceptable is selected from the group consisting of water(e.g., deionized, distilled water); emulsions (e.g., oil-in-wateremulsion, water-in-oil emulsion); alcohols (e.g., C₁₋₄ straight orbranched chain alcohols such as ethyl alcohol, propyl alcohol, isopropylalcohol, butyl alcohol); glycols (e.g., ethylene glycol, propyleneglycol, butylene glycol, pentylene glycol, hexylene glycol, dipropyleneglycol, ethoxydiglycol); glycerin; butyl cellosolve and mixturesthereof. More preferably, the personal care formulation of the presentinvention, comprises 30 to 92 wt % (preferably, 35 to 92 wt %; morepreferably, 40 to 80 wt %) of a cosmetically acceptable carrier; whereinthe cosmetically acceptable carrier includes water (preferably, at leastone of deionized water and distilled water; more preferably, deionized,distilled water).

Preferably, the personal care formulation of the present invention,further comprises a suncare active. More preferably, the personal careformulation of the present invention, comprises 0.1 to 70 wt %(preferably, 5 to 65 wt %; more preferably, 7.5 to 60 wt %; mostpreferably, 10 to 55 wt %) of a suncare active. More preferably, thepersonal care formulation of the present invention comprises 0.1 to 70wt % (preferably, 5 to 65 wt %; more preferably, 7.5 to 60 wt %; mostpreferably, 10 to 55 wt %) of a suncare active; wherein the suncareactive is a UV radiation absorbing agent. Still more preferably, thepersonal care formulation of the present invention, comprises 0.1 to 70wt % (preferably, 5 to 65 wt %; more preferably, 7.5 to 60 wt %; mostpreferably, 10 to 55 wt %) of a suncare active, wherein the suncareactive is a UV radiation absorbing agent selected from the groupconsisting of physical blockers (e.g., red petrolatum, titanium dioxide,zinc oxide) and chemical absorbers (e.g.,1-(4-methoxyphenol)-3-(4-tert-butylphenyl)propane-1,3-dione (INCI: ButylMethoxydibenzoylmethane); 2-hydroxy-4-methoxybenzophenone (INCI:Benzophenone-3); dioxybenzone; sulisobenzone; menthyl anthranilate;para-aminobenzoic acid; amyl paradimethylaminobenzoic acid; octylpara-dimethylaminobenzoate; ethyl 4-bis (hydroxypropyl)para-aminobenzoate; polyethylene glycol (PEG-25) para-aminobenzoate;ethyl 4-bis (hydroxypropyl) aminobenzoate; diethanolaminepara-methyoxycinnamate; 2-ethoxyethyl para-methoxycinnamate; ethylhexylpara-methoxycinnamate; octyl para-methoxycinnamate; isoamylpara-methoxycinnamate; 2-ethylhexyl-2-cyano-3,3-diphenyl-acrylate;2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate (INCI: octocrylene);2-ethylhexyl-2-hydroxybenzoate (INCI: Ethylhexyl Salicylate);homomenthyl salicylate; glyceryl aminobenzoate; triethanolaminesalicylate; digalloyl trioleate; lawsone with dihydroxyacetone;2-phenylbenzimidazole-5-sulfonic acid; 4-methylbenzylidine camphor;avobenzone; triazines; benzotriazoles; vinyl group-containing amides;cinnamic acid amides; sulfonated benzimidazoles);3,3,5-trimethylcyclohexyl 2-hydroxybenzoate (INCI: Homosalate). Yet morepreferably, the personal care formulation of the present invention,comprises 0.1 to 70 wt % (preferably, 5 to 65 wt %; more preferably, 7.5to 60 wt %; most preferably, 10 to 55 wt %) of a suncare active, whereinthe suncare active is a UV radiation absorbing agent comprises a mixtureof UV radiation absorbing agents. Yet still more preferably, thepersonal care formulation of the present invention, comprises 0.1 to 70wt % (preferably, 5 to 65 wt %; more preferably, 7.5 to 60 wt %; mostpreferably, 10 to 55 wt %) of a suncare active, wherein the suncareactive is a UV radiation absorbing agent is a mixture of UV absorbingagents including at least one of1-(4-methoxyphenol)-3-(4-tert-butylphenyl)propane-1,3-dione;2-ethylhexyl-2-hydroxybenzoate;2-ethyhexyl-2-cyano-3,3-diphenyl-2-propenoate;2-hydroxy-4-methoxybenzophenone and 3,3,5-trimethylcyclohexyl2-hydroxybenzoate. Most preferably, the personal care formulation of thepresent invention, comprises 0.1 to 70 wt % (preferably, 5 to 65 wt %;more preferably, 7.5 to 60 wt %; most preferably, 10 to 55 wt %) of asuncare active, wherein the suncare active is a UV radiation absorbingagent is a mixture of UV absorbing agents including1-(4-methoxyphenol)-3-(4-tert-butylphenyl)propane-1,3-dione;2-ethylhexyl 2-hydroxybenzoate;2-ethyhexyl-2-cyano-3,3-diphenyl-2-propenoate and2-hydroxy-4-methoxybenzophenone.

Preferably, the personal care formulation of the present invention,further comprises 0 to 20 wt % (preferably, 0.5 to 15 wt %; morepreferably, 1 to 10 wt %; most preferably, 2 to 5 wt %) of a SPFbooster. Preferably, the SPF booster is not an active ingredient, but isdesigned to enhance the effectiveness of the sunscreen actives presentin the formulation. Suitable SPF boosters include, but are not limitedto, styrene/acrylates copolymer, sodium bentonite, highly purified whitesodium bentonite, montmorillonite, hydrogel, or any combinationsthereof. A particularly preferred styrene/acrylates copolymer for use inthe suncare formulation of the present invention is sold under the tradename SunSpheres® by The Dow Chemical Company.

Preferably, the personal care formulation of the present invention,further comprises: a color ingredient. More preferably, the personalcare formulation of the present invention, further comprises a coloringredient; wherein the color ingredient is selected from the groupconsisting of inorganic pigments, organic pigments, aqueous pigmentdispersions and mixtures thereof. Still more preferably, the personalcare formulation of the present invention, further comprises a coloringredient; wherein the color ingredient is selected from the groupconsisting of Ext. D&C Yellow No. 2, Ext. D & C Violet No. 2, FD&C RedNo. 4, FD&C Red No. 40, FD&C Yellow No. 5, FD&C Yellow No. 6, FD&C GreenNo. 3, FD&C Blue No. 1, D&C Yellow No. 7, D&C Yellow No. 8, D&C YellowNo. 10, D&C Yellow No. 11, D&C Violet No. 2, D&C Red No. 6, D&C Red No.7, D&C Red No. 17, D&C Red No. 21, D&C Red No. 22, D&C Red No. 27, D&CRed No. 28, D&C Red No. 30, D&C Red No. 31, D&C Red No. 34, D&C Red No.33, D&C Red No. 36, D&C Green No. 5, D&C Green No. 6, D&C Green No. 8,D&C Blue No. 4, D&C Orange No. 4, D&C Orange No. 5, D&C Orange No. 10,D&C Orange No. 11, D&C Brown No. 1, Aluminum powder, Annatto, Bismuthcitrate, Bismuth Oxychloride, Bronze powder, Caramel, Carmine,(3-Carotene, Chromium hydroxide green, Chromium oxide green, Copperchlorophyllin, Copper powder, Dihydroxyacetone, Ferric Ammoniumferrocyanide, Ferric ferrocyanide, Guanine, Iron oxide, ManganeseViolet, Mica, Silver, Titanium Dioxide, Ultramarine, Zinc Oxide andmixtures thereof. Still more preferably, the personal care formulationof the present invention, further comprises a color ingredient; whereinthe color ingredient includes at least one iron oxide. Most preferably,the personal care formulation of the present invention, furthercomprises a color ingredient; wherein the color ingredient includes amixture of iron oxides.

Preferably, the personal care formulation of the present invention,further comprises a color ingredient, wherein the color ingredient is apigment. More preferably, the personal care formulation of the presentinvention, further comprises a color ingredient, wherein the coloringredient is a pigment and wherein the pigment has a surface treatment.Still more preferably, the personal care formulation of the presentinvention, further comprises a color ingredient; wherein the coloringredient is a pigment; wherein the pigment has a surface treatment andwherein the surface treatment is formed through treatment of the pigmentwith a surface treatment agent selected from the group consisting of analkyl silane, a halogenated phosphonate, a halogenated organosilane or acombination thereof. Most preferably, the personal care formulation ofthe present invention, further comprises a color ingredient; wherein thecolor ingredient is a pigment; wherein the pigment has a surfacetreatment and wherein the surface treatment is formed through treatmentof the pigment with a surface treatment agent selected from the groupconsisting of sodium perfluorohexylethylphosphonate, triethoxycaprylylsilane, perfluorooctyltriethoxysilane and mixtures thereof.

Preferably, the personal care formulation of the present invention,optionally, further comprises an optional additive. More preferably, thecolor cosmetic formulation of the present invention, further comprisesan optional additive, wherein the optional additive is selected from thegroup consisting of water proofing agents, emollients, preservatives,antioxidants, fragrances, humectants, rheology modifiers, aestheticmodifiers, vitamins, skin protectants, oils, emulsifiers, surfactants,pearlizers, consistency factors, thickeners, super fatting agents,stabilizers, polymers, silicone compounds, fats, waxes, lecithins,phospholipids, fillers, light management powders and particles, andmixtures thereof.

Preferably, the personal care formulation of the present invention has apH of 4 to 9. More preferably, the personal care formulation of thepresent invention has a pH of 4.5 to 8.5. Still more preferably, thepersonal care formulation of the present invention has a pH of 5.0 to8.0. Most preferably, the personal care formulation of the presentinvention has a pH of 5.5 to 7.5.

Preferably, the personal care formulation of the present invention isprovided a product form selected from the group consisting of a cream,an aqueous solution, an oil, an ointment, a paste, a gel, a lotion, amilk, a foam, a stick and a suspension.

The multistage polymer of the present invention can be prepared byconventional polymerization techniques, such as, for example, byemulsion polymerization. Preferably, the multistage polymer of thepresent invention is an emulsion polymer.

The personal care formulation of the present invention is useful for atleast one of treating (e.g., moisturizing; protecting from harmfuleffects of exposure to the sun) and enhancing the appearance of skinthrough application to the skin. Preferably, the personal careformulation of the present invention applies easily to the skin. Whenprovided in the form of a color cosmetic formulation, the personal careformulation of the present invention leaves a clear vivid color thatremains in place at least through the work day and preferablythereafter.

Some embodiments of the present invention will now be described indetail in the following Examples.

The monomer abbreviations used in the Examples are described in TABLE 1.

TABLE 1 Abbreviation Monomer BA Butyl Acrylate BMA Butyl MethacrylateIBMA Isobutyl Methacrylate EHA 2-Ethylhexyl Acrylate EHMA 2-EthylhexylMethacrylate MMA Methyl Methacrylate MAA Methacrylic Acid ALMA AllylMethacrylate MD′M-ALMA

M′DM-IPMA

Comparative Example CS1: Single Stage Polymer

A 1-liter round-bottom flask equipped with an overhead stirrer,thermocouple, condenser and inlets for the addition of monomer andinitiators was charged with deionized water (150.0 g), sodium dodecylsulfonate surfactant (3.3 g of a 23% DS-4) and sodium carbonate (1.1 g).The flask contents were then stirred and heated at 85° C. A monomeremulsion was prepared by charging deionized water (81.1 g) and sodiumdodecyl sulfonate surfactant (3.1 g of 23% DS-4) to a container and setto stir. After the surfactant was incorporated into the water, butylacrylate (BA)(50 g), ethylhexyl acrylate (EHA)(100 g), methylmethacrylate (MMA)(96.3 g), methacrylic acid (MAA)(3.8 g) and allylmethacrylate (ALMA)(0.2 g) were added slowly to the stirring mixture inthe container. A cofeed catalyst solution was also prepared by chargingsodium persulfate (0.25 g) and deionized water (22 g) in anothercontainer. When the flask contents reached a temperature of 85° C., 10 gof the above prepared monomer emulsion was charged to the flask,followed with a deionized water rinse (10 g) water rinse, followed by aninitiator solution of sodium persulfate (0.9 g) in deionized water (5.7g). After initial polymerization and at 85° C., a monomer emulsioncofeed to the flask of the above prepared monomer emulsion was begun ata rate of 1.97 g/min for 15 minutes and then at a rate of 3.93 g/min.for the next 75 minutes. Simultaneously, with the monomer emulsioncofeed the catalyst cofeed was begun at a rate of 0.24 g/min for 92minutes. At the completion of the cofeeds, the flask contents werechased to reduce the amount of residual monomers to provide the productsingle stage polymer.

Comparative Example CS2: Dendritic Silicone-Grafted Vinyl Copolymer

A flask equipped with an overhead stirrer, thermocouple, condenser andinlets for the addition of monomer and initiators was charged withcarbosiloxane dendrimer (150 parts) with the following structure

methyl methacrylate (MMA)(99 parts), n-butyl methacrylate (BMA)(51parts) and 2-phenoxyethanol (9 parts). To the flask contents was thenwas added laureth-1 phosphate (7 parts), sodium hydroxide solution (4parts, 20%) and deionized water (676 parts). The flask contents werethen emulsified and dispersed using a homogenizer. The flask contentswere then heated to 80° C., under a nitrogen. Upon reaching temperature,potassium persulfate (2.2 parts) was added to the flask contents whilemaintaining the temperature controller at 80° C. After three hours afterthe potassium persulfate addition,2,2′-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] tetrahydrate (2.2parts) was added to the flask contents while maintaining the temperaturecontroller at 80° C. The flask contents were allowed to stir for threeadditional hours while maintaining the temperature controller at 80° C.,to provide the product dendritic silicone-grafted vinyl copolymer.

Example S1: Multistage Polymer

A 2-liter round-bottom flask (equipped with an overhead stirrer,thermocouple, condenser and inlets for the addition of monomer andinitiators) was charged with deionized water (252.0 g), 50% CAVASOL™ W7MTL (cyclodextrin from Wacker Fine Chemicals) (5.3 g), 23% DS-4surfactant (5.3 g) (A-16-22 from Stepan) and sodium carbonate (1.8 g).The flask contents were stirred and heated to 85° C.

An acrylate rich monomer emulsion was prepared by charging deionizedwater (103.8 g) and 23% DS-4 surfactant (4.0 g) to a first container andset to stir. Once the surfactant was incorporated into the water thefollowing monomers were added slowly to the first container withcontinued stirring: BA (64 g), EHA (128.0 g), MMA (123.2 g), methylacrylic acid MAA (4.8 g) and ALMA (0.24 g).

A carbosiloxane rich monomer emulsion was prepared by charging deionizedwater (26.0 g) and 23% DS-4 surfactant (1.0 g) to a second container andset to stir. Once the surfactant was incorporated into the water thefollowing monomers were added slowly to the second container withcontinued stirring: MD′M-ALMA (64 g), MMA (14.8 g) and MAA (1.2 g). Thecarboxiloxane rich monomer emulsion was further emulsified using thehomogenization at 10 K rpm for 10 min.

A cofeed catalyst solution was prepared containing sodium persulfate(0.8 g) and deionized water (35.2 g).

A cofeed buffer solution was prepared containing sodium carbonate (0.8g) and deionized water (35.2 g).

At a reaction set point temperature of 85° C., 12.8 g of the acrylaterich monomer emulsion from the first container along with a deionizedwater rinse (16.0 g) was charged to the flask contents. An initiatorsolution of sodium persulfate (1.8 g) in deionized water (12.0 g) wasthen added to the flask contents. After the initial polymerization, theremainder of the acrylate rich monomer emulsion in the first containerwas cofeed to the flask contents at a rate of 3.08 g/min. for 15 minutesand then at 6.15 g/min for 60 minutes. Simultaneously with the acrylaterich monomer emulsion cofeed, the cofeed catalyst solution and thecofeed buffer solution were added to the reactor contents at a rate of0.39 g/min. for 92 minutes.

Following the addition of the acrylate rich monomer emulsion, thecarbosiloxane rich monomer emulsion in the second container was added tothe reactor contents at a rate of 7.23 g/min for 15 minutes. Aftercompletion of the various feeds, the contents of the flask were chasedto reduce the amount of residual monomers, providing the productmultistage polymer.

Example S2: Multistage Polymer

The multistage polymer of Example S2 was prepared in the same fashion asthe multistage polymer of Example S1 except that the carbosiloxane richmonomer emulsion was added to the flask contents as a shot. Afteraddition, the reaction mixture was held steady with stirring at 85° C.for 20 minutes. At the end of the hold time, catalyst and buffer co-feedwas restarted. At the completion of catalyst cofeed, the flask contentswere chased to reduce the amount of residual monomers, providing theproduct multistage polymer.

Examples S3-S19: Multistage Polymer

Multistage polymers were prepared substantially as described in ExampleS1 the appropriate changes being made reflecting the total wt % of theacrylate rich stage and the carbosiloxane rich stage in the respectivemultistage polymers of Examples S3-S19 with the acrylate rich stagemonomers and the carbosiloxane rich stage monomers in the respectivestages as noted in TABLE 2.

TABLE 2 Multistage polymer Carbosiloxane rich state Acrylate rich stageMonomer (wt %) Total Monomer (wt %) Total MD′M- MD′M- Ex. wt % BA BMAIBMA EHA EHMA MMA MAA ALMA wt % MAA MMA ALMA IPMA S1 80 20 — — 40 — 38.51.5 0.075 20 1.5 18.5 80 — S2 80 20 — — 40 — 38.5 1.5 0.075 20 1.5 18.580 — S3 90 20 — — 40 — 38.5 1.5 0.075 10 1.5 18.5 80 — S4 70 20 — — 40 —38.5 1.5 0.075 30 1.5 18.5 80 — S5 80 20 — — 40 — 38.5 1.5 0.075 20 1.533.5 65 — S6 80 — — — 40 — 58.5 1.5 0.075 20 1.5 18.5 80 — S7 80 20 — —— — 78.5 1.5 0.075 20 1.5 18.5 80 — S8 80 20 — — 40 — 38.5 1.5 0.075 201.5 18.5 — 80 S9 80 — 20 — 40 — 38.5 1.5 0.075 20 1.5 18.5 80 — S10 80 —— 20 40 — 38.5 1.5 0.075 20 1.5 18.5 80 — S11 70 — 20 — 40 — 38.5 1.50.075 30 1.5 18.5 80 — S12 70 — — 20 40 — 38.5 1.5 0.075 30 1.5 18.5 80— S13 80 20 — — — 40 38.5 1.5 0.075 20 1.5 18.5 80 — S14 70 20 — — — 4038.5 1.5 0.075 30 1.5 18.5 80 — S15 70 50 23.5 — — — 25 1.5 0.075 30 1.518.5 80 — S16 70 40 33.5 — — — 25 1.5 0.075 30 1.5 18.5 80 — S17 80 4033.5 — — — 25 1.5 0.075 20 1.5 18.5 80 — S18 80 30 43.5 — — — 25 1.50.075 20 1.5 18.5 80 — S19 80 20 53.5 — — — 25 1.5 0.075 20 1.5 18.5 80—

Polymer Properties

The product multistage polymers prepared according to ComparativeExample CS1 and Examples S1-S19 were analyzed for percent solids, pH,mean particle size (using Brookhaven Instruments BI-90 particle sizeanalyzer) and glass transition temperature, Tg, as measured using a TAinstruments model 2920 Differential Scanning calorimeter (DSC). Theresults are provided in TABLE 3.

TABLE 3 Example % solids pH PS (nm) Tg (° C.) CS1 41.04 5.87 117.1 −10S1 43.38 5.60 145.2 −7.6 S2 39.36 5.77 201.5 −12.3 S3 39.41 5.87 122.1−7.5 S4 38.90 5.74 130.4 −8.9 S5 38.06 5.74 139.0 −11.6 S6 39.37 5.77126.5 28.5 S7 40.65 5.72 153.0 77.4 S8 38.52 5.63 148.9 −11.4 S9 37.625.37 138.9 7.2 S10 39.71 5.60 137.8 15.3 S11 39.08 5.62 136.1 5.8 S1238.44 5.56 128.9 15.3 S13 37.65 5.56 130.4 24.2 S14 39.26 5.52 128.225.7 S15 46.78 5.40 145.0 −6.2 S16 47.01 5.40 149.4 4.4 S17 45.10 5.70150.5 2.7 S18 47.18 — 150.4 12.8 S19 46.36 — 146.2 25.6

Formulation Examples G1 and G2: Generic Suncare Formulations

Generic suncare personal care formulations were prepared having thegeneric formulations according to Formulation Examples G1 and G2 notedin TABLE 4. The carbomer and some deionized water were added to a flaskand mixed until the carbomer was hydrated before adding the remainder ofthe Phase I ingredients. The flask contents were then heated at 75° C.with mixing. The Phase II ingredients were combined in a separatecontainer while being heated at 75° C. with mixing until dissolved. ThePhase II ingredients were then added to the flask contents with mixinguntil uniform. The Phase III ingredients were then added to the flaskcontents with mixing until uniform. The flask contents were then removedfrom the heating source and cooled. When the flask contents cooled below60° C., the Phase IV ingredients were added to the flask contents withmixing until uniform. When the flask contents cooled to below 40° C.,the Phase V ingredients were added to the flask contents with continuedmixing until the flask contents reached ambient room temperature. Theflask contents were then pH adjusted to a pH of 5.5 to 7.5, asnecessary.

TABLE 4 Generic Formulations Form. Form. Ex. G1 Ex. G2 Ingredient Partsby weight Parts by weight Phase INCI name (pbW) (pbW) Deionized waterremainder to 100 remainder to 100 I Carbomer¹ 0.20 0.20 I Disodium EDTA²0.10 0.10 I Propylene Glycol 2.00 2.00 II Avobenzone 3.00 3.00 IIOxybenzone 6.00 6.00 II Octyl Salicylate 5.00 5.00 II Octocrylene 10.0010.00 II Hydrogenated Polydecene³ 7.00 7.00 II C₁₂₋₁₅ Alkyl Benzoate⁴5.00 5.00 II PEG 40 Stearate⁵ 1.00 1.00 II Glyceryl Stearate⁶ 1.00 1.00II Cetearyl Alcohol, 1.00 1.00 Cetereth-20⁷ III Triethanolamine, 99%0.35 0.35 IV Polymer to be tested (on 1.00 3.00 polymer solids basis) VPreservative 1.00 1.00 ¹Available from Rita under the tradenameAcritamer 980. ²Available from The Dow Chemical Company under thetradenamer Versene NA. ³Available from Rita under the tradenameRitadecene 20. ⁴Available from Rita under the tradename Ritamollient TN.⁵Available from Rita under the tradename Ritox 52. ⁶Available from Ritaunder the tradename Rita GMS. ⁷Available from Protameen under thetradename Procol CS-20-D.

Comparative Examples C1-C4 and Examples 1-26: Suncare Formulations

The suncare formulations of (a) Comparative Examples C1-C2 and Examples1-13 and (b) Comparative Examples C3-C4 and Examples 14-26 were preparedaccording to Formulation Examples G1 and G2, respectively with the testpolymer as noted in TABLE 5.

In-Vitro SPF Measurements

The suncare formulations prepared according to Comparative ExamplesC1-C4 and Examples 1-26 were each allowed to settle for one week beforein-vitro SPF measurements. The in-vitro SPF performance of each of thesuncare formulations was then tested in triplicate using an in-vitrotechnique according to the following protocol.

The substrate used for the in-vitro SPF measurements was a rough PMMAsubstrate (6 μm—HD6 available from Schonberg GMBH & Co. KG). The suncareformulations to be tested were each applied to three separate rough PMMAsubstrates using an RDS #7 wire draw down bar to provide a uniform layerof the suncare formulation over the surface of the PMMA substrate at arate of 1.2 to 1.3 mg/cm². Each deposited layer of suncare formulationwas allowed to dry for fifteen (20) minutes under ambient conditions inthe laboratory. The UV absorption of each dried layer of suncareformulation between 290 nm and 400 nm was then measured at six (6)separate points using a Labsphere UV-2000S Spectrometer. The in-vitroSPF value for each suncare formulation prepared according to ComparativeExamples C1-C4 and Examples 1-26 was then calculated based on theresults of the UV absorption measurements. The average from thetriplicate samples of each suncare formulation prepared according toComparative Examples C1-C4 and Examples 1-26 is reported in TABLE 5.

Water Resistance (In-Vitro SPF Retention)

The test substrates from the original in-vitro SPF measurementsdiscussed above with applied formulations prepared according toComparative Examples C1-C4 and Examples 1-26 were then each immersed ina controlled temperature water bath (30° C.) with a propeller agitationspeed of 300 rpm for two hours. The substrates were then removed fromthe water bath and left to dry under ambient laboratory conditions for20-30 minutes after which the in-vitro SPFs for each suncare formulationwas measured and compared to its original in-vitro SPF measurement andthe two hour SPF retention was calculated as reported in TABLE 5.

TABLE 5 Formulation in-vitro SPF Example Example Polymer SPF Retention(%) C1 G1 SC1 150 43 C2 G1 SC2 236 36 C3 G2 SC1 230 49 C4 G2 SC2 257 43 1 G1 S1 313 60  2 G1 S2 411 74  3 G1 S3 343 48  4 G1 S4 348 64  5 G1 S5332 59  6 G1 S6 301 70  7 G1 S7 316 51  8 G1 S8 305 82  9 G1 S9 363 6110 G1 S10 337 67 11 G1 S13 295 65 12 G1 S15 306 58 13 G1 S16 239 84 14G2 S1 335 59 15 G2 S2 390 73 16 G2 S3 468 57 17 G2 S4 402 57 18 G2 S5410 69 19 G2 S6 371 63 20 G2 S7 382 75 21 G2 S8 403 84 22 G2 S9 416 5723 G2 S10 389 80 24 G2 S13 378 74 25 G2 S15 407 64 26 G2 S16 319 84

Formulation Example G3: Generic Color Cosmetic Formulation

Color cosmetic formulations were prepared having the genericformulations according to Formulation Example G3 noted in TABLE 6. ThePhase A ingredients were added to a beaker and mixed until uniform. ThePhase C ingredients were combined in a separate container with mixinguntil uniform. The Phase D ingredients were combined in a separatecontainer with mixing until uniform. The Phase D ingredients were thenadded to the beaker and mixed with the Phase A ingredients. The Phase Cingredients were then slowly added to the contents of the beaker. ThePhase B polymer ingredient was then slowly added to the contents of thebeaker with mixing. The Phase F deionized water ingredient was thenadded to the beaker. The Phase E ingredient was then added to thecontents of the beaker. The beaker contents were then mixed untiluniform to provide the product color cosmetic formulation.

TABLE 6 Parts by Phase Ingredient INCI name weight (pbW) A Lauryl PEG-10Tris(trimethylsiloxy)silyethyl 5 Dimeticone¹ A Isododecane² 11 B Polymerto be tested (on a polymer solids basis) 4 C Deionized water 41 C Sodiumchloride 0.85 C Glycerin 4.25 C Phenoxyethanol (and) Ethylhexylglycerin³0.85 D Iron Oxide dimethicone⁴ 0.06 D Iron Oxide (CI 77491),dimethicone⁵ 0.2 D Iron Oxide (CI 77492), dimethicone⁶ 0.9 D TitaniumDioxide, dimethicone⁷ 4.9 D Caprylyl Methicone⁸ 2.8 E Isododecane² 9 FDeionized water q.s. 100 ¹Available from The Dow Chemical Company underthe tradename Dowsil ™ ES-5300. ²Available from Presperse under thetradename Permethyl ® 99A. ³Available from Schulke Inc. under thetradename euxyl ® PE 9010. ⁴Available from Miyoshi America undertradename SAT-B-335198. ⁵Available from Miyoshi America under tradenameSAT-R-338075. ⁶Available from Miyoshi America under tradenameSAT-Y-338073. ⁷Available from Miyoshi America under tradenameSAT-TRI-77891. ⁸Available from The Dow Chemical Company under thetradename Dowsil ™ FZ-3196.

Comparative Examples C5-C7 and Examples 27-28: Color CosmeticFormulations

The color cosmetic formulations of Comparative Examples C5-C7 andExamples 27-28 were prepared according to Formulation Example G3 withvarying test polymer as noted in TABLE 7.

Wear Resistance

The color cosmetic formulations prepared according to ComparativeExamples C5-C7 and Examples 27-28 were each coated on two separate whitevinyl charts (available from Leneta) using a doctor blade filmapplicator with the gap set at 6 mils (0.1524 mm) and allowed to dry at22° C. for at least 48 hours. The color reading of each sample was thenmeasured by colorimeter (Ocean Optics). The wear resistance of thedeposited film of color cosmetic formulations was characterized by thechange (ΔE) before and after abrasion with a pre-cut bath towel (55mm×45 mm). The bath towel was fixed to a moving robotic part that movesback and forth periodically at a constant speed. The film was abraded bythe bath towel by 3 wear cycles under a pressure of approximately 600Pa, each wear cycle lasts 6 seconds. Readings were taken from five pointon each deposited film. The average of the five readings from each ofthe duplicate deposited films is provided in TABLE 7.

TABLE 7 Example Polymer AE Comp. Example C5 Caprylyl Methicone¹ 9.8Comp. Example C6 SC1 4.8 Comp. Example C7 SC2 5.2 Example 27 S6 3.5Example 28 S17 3.1 ¹Available from The Dow Chemical Company under thetradename Dowsil ™ FZ-3196.

We claim:
 1. A personal care formulation, comprising: a multistagepolymer, comprising: (a) an acrylate rich stage comprising: 88 to 100 wt%, based on weight of the acrylate rich stage, of structural units of amonoethylenically unsaturated non-ionic, acrylate rich stage monomer,wherein the monoethylenically unsaturated non-ionic, acrylate rich stagemonomer is selected from the group consisting of C₁₋₂₂ alkyl(meth)acrylates and mixtures thereof; 0 to 10 wt %, based on weight ofthe acrylate rich stage, of structural units of a monoethylenicallyunsaturated carboxylic acid, acrylate rich stage monomer; and 0 to 2 wt%, based on weight of the acrylate rich stage, of structural units of amultiethylenically unsaturated, acrylate rich stage monomer having atleast two ethylenically unsaturated groups per molecule; and (b) acarbosiloxane rich stage, comprising: 0 to 90 wt %, based on weight ofthe carbosiloxane rich stage, of structural units of a vinyl monomer;and 10 to 100 wt %, based on weight of the carbosiloxane rich stage, ofstructural units of a carbosiloxane monomer of formula (I)

wherein a is 0 to 3; wherein d is 0 or 1; wherein each R¹ isindependently selected from the group consisting of a hydrogen, a C₁₋₁₀alkyl group and an aryl group; wherein each R² is independently selectedfrom the group consisting of a hydrogen and a C₁₋₁₀ alkyl group; whereineach R⁸ is a —O—Si(CH₃)₂—O—Si(CH₃)₃ group; wherein Y is selected fromthe group consisting of formula (II), (III) and (IV)

wherein each R⁴ and R⁶ are independently selected from the groupconsisting of a hydrogen and a methyl group; wherein each R³ and R⁵ areindependently a C₁₋₁₀ alkylene group; wherein each R⁷ is independently aC₁₋₁₀ alkyl group; wherein b is 0 to 4 and wherein c is 0 or
 1. 2. Thepersonal care formulation of claim 1, wherein the monoethylenicallyunsaturated non-ionic, acrylate rich stage monomer is selected from thegroup consisting of a mixture of (i) 40 to 75 wt % of a C₁₋₄ alkyl(meth)acrylate and (ii) 25 to 60 wt % of a C₆₋₂₂ alkyl (meth)acrylateselected from the group consisting of ethylhexyl (meth)acrylate, lauryl(meth)acrylate, stearyl (meth)acrylate, cetyl-eicosyl (meth)acrylate,behenyl (meth)acrylate and mixtures thereof; wherein themonoethylenically unsaturated carboxylic acid, acrylate rich stagemonomer is selected from the group consisting of acrylic acid,methacrylic acid, itaconic acid, crotonic acid and mixtures thereof;wherein the multiethylenically unsaturated, acrylate rich stage monomerhaving at least two ethylenically unsaturated groups per molecule isselected from the group consisting of divinylaromatic compounds,di-(meth)acrylate esters, tri-(meth)acrylate esters,tetra-(methacrylate)esters, di-allyl ethers, tri-allyl ethers,tetra-allyl ethers, di-allyl esters, tri-allyl esters, tetra-allylesters, allyl (meth)acrylate and mixtures thereof; wherein the vinylmonomer is selected from the group consisting of a mixture ofmethacrylic acid and methyl methacrylate; wherein a is 1; wherein d is0; wherein each R¹ is a methyl group; wherein each R² is a methyl group;wherein Y is of formula (II); wherein each R³ is a C₃₋₅ alkylene group;and wherein each R⁴ is a methyl group.
 3. The personal care formulationof claim 2, further comprising a cosmetically acceptable carrier.
 4. Thepersonal care formulation of claim 3, further comprising a coloringredient.
 5. The personal care formulation of claim 3, furthercomprising a suncare active.
 6. The personal care formulation of claim5, having 30 to 92 wt % of the cosmetically acceptable carrier; 0.1 to10 wt %, on a solids basis, of the multistage polymer; and 0.1 to 70 wt% of the suncare active.
 7. The personal care formulation of claim 6,wherein the cosmetically acceptable carrier includes water.
 8. Thepersonal care formulation of claim 7, wherein the suncare active is a UVradiation absorbing agent is selected from the group consisting ofphysical blockers and chemical absorbers.
 9. The personal careformulation of claim 8, wherein the suncare active is a UV radiationabsorbing agent selected from the group consisting of red petrolatum;titanium dioxide; zinc oxide;1-(4-methoxyphenol)-3-(4-tert-butylphenyl)propane-1,3-dione;2-hydroxy-4-methoxybenzophenone; dioxybenzone; sulisobenzone; menthylanthranilate; para-aminobenzoic acid; amyl paradimethylaminobenzoicacid; octyl para-dimethylaminobenzoate; ethyl 4-bis (hydroxypropyl)para-aminobenzoate; polyethylene glycol (PEG-25) para-aminobenzoate;ethyl 4-bis (hydroxypropyl) aminobenzoate; diethanolaminepara-methyoxycinnamate; 2-ethoxyethyl para-methoxycinnamate; ethylhexylpara-methoxycinnamate; octyl para-methoxycinnamate; isoamylpara-methoxycinnamate; 2-ethylhexyl-2-cyano-3,3-diphenyl-acrylate;2-ethylhexyl-2-cyano-3,3-diphenyl-2-propenoate;2-ethylhexyl-2-hydroxybenzoate; homomenthyl salicylate; glycerylaminobenzoate; triethanolamine salicylate; digalloyl trioleate; lawsonewith dihydroxyacetone; 2-phenylbenzimidazole-5-sulfonic acid;4-methylbenzylidine camphor; avobenzone; triazines; benzotriazoles;vinyl group-containing amides; cinnamic acid amides; sulfonatedbenzimidazoles); 3,3,5-trimethylcyclohexyl 2-hydroxybenzoate andmixtures thereof.
 10. The suncare formulation of claim 9, wherein thesuncare active is a UV radiation absorbing agent is a mixture of UVabsorbing agents including1-(4-methoxyphenol)-3-(4-tert-butylphenyl)propane-1,3-dione;2-ethylhexyl 2-hydroxybenzoate;2-ethyhexyl-2-cyano-3,3-diphenyl-2-propenoate and2-hydroxy-4-methoxybenzophenone; and wherein R³ is a C₃ alkylene.